EP1812235A1 - Capstock acrylique - Google Patents

Capstock acrylique

Info

Publication number
EP1812235A1
EP1812235A1 EP05818155A EP05818155A EP1812235A1 EP 1812235 A1 EP1812235 A1 EP 1812235A1 EP 05818155 A EP05818155 A EP 05818155A EP 05818155 A EP05818155 A EP 05818155A EP 1812235 A1 EP1812235 A1 EP 1812235A1
Authority
EP
European Patent Office
Prior art keywords
layer
multilayer structure
iii
meth
pmma
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05818155A
Other languages
German (de)
English (en)
French (fr)
Inventor
Pierre Gerard
Olivier Guerret
Christophe Le Crom
Patrick Delprat
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP1812235A1 publication Critical patent/EP1812235A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/406—Bright, glossy, shiny surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2509/00—Household appliances
    • B32B2509/10—Refrigerators or refrigerating equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2590/00—Signboards, advertising panels, road signs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars

Definitions

  • the protective layer (I) comprises a PMMA.
  • the PMMA-index melt (measured at 230 ° C., under a load of 3.8 kg) is between 0.5 and 10 g / 10 min, advantageously between 1 and 5 g / 10 min.
  • the protective layer (I) serves to protect the structural plastic against scratches, chemicals and against aging. It also improves the gloss of certain structural plastics.
  • ABS has a gloss only of the order of 40-50 at an angle of 60 °.
  • a gloss between 70 and 95, preferably between 85 and 90 can be obtained via the protective layer (I).
  • the impact modifiers used are for example: DURASTRENGTH ® D320 from Arkema; IRH 70 from MITSUBISHI (soft / hard bilayer with butadiene-butyl acrylate copolymer soft core and hard PMMA bark); KM-355 from ROHM and HAAS.
  • the mixture M B comprises: from 60% to 100%, advantageously from 70% to 100%, preferably from 80% to 100% of at least one (meth) acrylic monomer having a T 3 of less than -5 ° C. for respectively
  • the intermediate ductile layer has the function of reinforcing the impact resistance of the plastic structure / protective layer assembly. Indeed, when applying a protective layer based on PMMA which is a brittle material, on a structural plastic, the impact resistance of the assembly is lower than that of the structural plastic alone and is substantially equivalent to that of the protective layer. A crack initiated in the PMMA layer propagates unabated to the structural plastic and damages it. In the presence of the intermediate ductile layer, the impact resistance of the assembly is maintained or even improved compared to the structural plastic because, in this case, the crack is stopped by the intermediate ductile layer.
  • the Lewis base is, for example, chosen from the following list: dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, anisole; 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-diisopropoxyethane, 1,2-dibutoxyethane, 1,2-diphenoxyethane, 1,2-dimethoxypropane, 1,2-diethoxypropane, 1,2-diisopropoxypropane, 1, 2-dibutoxypropane, 1,2-diphenoxypropane, 1,3-dimethoxypropane, 1,3-diethoxypropane, 1,3-diisopropoxypropane, 1,3-dibutoxypropane, 1,3-diphenoxypropane, 1,4-dimethoxybutane, 1,4 diethoxybutane, 1,4-diisopropoxybutane, 1,4-dibutoxybutane, 1,4-diphenoxybutane,
  • the NMP type polymerization is used to prepare the block copolymer in the presence of an alkoxyamine of formula ZT n in which Z denotes a multivalent group and T denotes a nitroxide.
  • Z denotes a multivalent group, that is to say a group capable of releasing several radical sites after activation. The activation in question occurs by breaking the covalent ZT bonds.
  • R 7 , R 8 and R 9 which are identical or different, have the same meanings as R 3 and R 4 of the formula (I), q, r and s are integers ranging from 1 to 10;
  • Rn has the same meaning as the radical Ri 0 of the formula (IV) and v is an integer between 2 and 6 wherein R 12 , R 13 and R 14 ; identical or different, represent a phenyl radical, optionally substituted with a halogen atom such as Cl, Br, or with a linear or branched alkyl radical having a number of carbon atoms ranging from 1 to 10; W is oxygen, sulfur, selenium, w is zero or 1;
  • R 15 -CH-CO-CH 2 -CH-R 16 (VII) wherein R 5 has the same meaning as R 3 of the formula (I), Ri ⁇ has the same meaning as R5 or Re of formula (II) ;
  • R 1 and R 6 which are identical or different, represent a hydrogen atom, a linear or branched alkyl radical having a number of carbon atoms ranging from 1 to 10, an aryl radical, optionally substituted with a halogen atom or a hetero atom.
  • R a and Rb denoting identical or different alkyl groups having from 1 to 40 carbon atoms, optionally linked to each other so as to form a ring and optionally substituted with hydroxyl, alkoxy or amino groups,
  • R L denoting a monovalent group of molar mass greater than 16 g / mol, preferably greater than 30 g / mol.
  • the group R 1 may, for example, have a molar mass of between 40 and 450 g / mol. It is preferably a phosphorus group of general formula (XI):
  • R L is a phosphonate group of formula:
  • R c and R d are two identical or different alkyl groups, optionally linked so as to form a ring, comprising from 1 to 40 carbon atoms, optionally substituted or not.
  • the R L group may also comprise at least one aromatic ring such as the phenyl radical or the naphthyl radical, substituted for example by one or more alkyl radicals comprising from 1 to 10 carbon atoms.
  • nitroxides of formula (X) are preferred because they make it possible to obtain good control of the radical polymerization of (meth) acrylic monomers as taught in WO 03/062293.
  • Alkoxyamines of formula (XIII) having a nitroxide of formula (X) are therefore preferred:
  • RL denotes a monovalent group of molar mass greater than 16 g / mol, preferably greater than 30 g / mol.
  • the group R L may for example have a molar mass of between 40 and 450 g / mol. It is preferably a phosphorus group of general formula (XI):
  • R L is a phosphonate group of formula:
  • N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide commonly referred to as SG1 for simplicity.
  • This nitroxide makes it possible to effectively control the polymerization of the (meth) acrylic monomers.
  • the alkoxyamines can be prepared by recipes described for example in US590549 or in FR99.04405.
  • the sequence B is prepared by heating the mixture M B in the presence of at least one alkoxyamine ZT n , the heating being carried out at a temperature sufficient to activate the alkoxyamine and polymerize the mixture M B until a conversion of at least 60%,
  • sequences A are prepared by heating the sequence B obtained in step 1 in the presence of the mixture M A , the heating being carried out at a temperature sufficient to activate the sequence B and polymerize the mixture M A.
  • the initiation of the polymerization leading to the sequence B is carried out with the alkoxyamine ZT n .
  • the initiation of the polymerization leading to the A sequences is achieved by the reactivation of the B sequence.
  • a nitroxide identical or different from that which is worn on the alkoxyamine.
  • the molar proportion of the added nitroxide relative to the alkoxyamine ZT n is between 0 and 20%, preferably between 0 and 10%.
  • the conversion to monomer (s) of the mixture M B in step 1 is between 60 and 100%.
  • the conversion is between 60 and 95%, advantageously between 70 and 95%.
  • the radical initiator is selected so that it has a temperature Ti / 2 , i h (i.e., the temperature to have a half-life time of 1 h) which is 0 C greater than the activation temperature of the alkoxyamine ZT n or of the sequence B.
  • the radical initiator may be an organic or inorganic initiator such as a persulfate.
  • the azobisisobutyronitrile or Luperox ® 546 are two examples of suitable radical initiators.
  • Each of the steps of the process can be carried out according to a mass process, in solution in a solvent or in an aqueous dispersed medium (emulsion, suspension).
  • An example of a process for the preparation of the BA n block copolymer in an aqueous dispersed medium in which the B sequence has previously been prepared by a mass process or in solution in a solvent comprises the following steps: a) the water is introduced, at least a dispersing agent, the sequence B and the mixture M A , b) the mixture M A is polymerized by heating at a temperature sufficient to activate the sequence B, c) recovering the block copolymer BA n .
  • the dispersing agent is a compound which stabilizes the emulsion or suspension. It may be for example a surfactant or a protective colloid.
  • radical initiator it is possible to introduce a radical initiator before and / or at the end of step b). If the radical initiator is introduced before step b), it is preferably chosen so that it does not interfere with sequence B in the polymerization of the mixture M A. It is preferably chosen so that its temperature T1 / 2, 1 h (that is to say, the temperature to have a half-life time of 1 h) is 20 ° C higher than the temperature of reactivation of sequence B.
  • the intermediate ductile layer (II) and the protective layer (I) may each comprise one or more additives chosen from:
  • matting agents which may be mineral fillers such as for example talc, calcium carbonate, titanium dioxide, zinc oxide or organic fillers such as for example crosslinked beads based on styrene and / or MMA (examples of such beads are given in EP 1174465).
  • the intermediate ductile layer (II) and the protective layer (III) may each comprise at least one anti-UV.
  • the proportion of anti-UV in the intermediate ductile layer (II) or in the protective layer (III) is from 0 to 10 parts, advantageously from 0.2 to 10 parts, preferably from 0.5 to 5 parts, anti-UV for 100 parts of polymer.
  • a list of useful UV-stabilizers can be found in the document "Plastics Additives and Modifiers Handbook, chap. 16, Environmental Protective Agents ", J. Edenbaum, Ed., Van Nostrand, pp. 208-271, incorporated by reference into the present application.
  • the anti-UV is a compound of the family of HALS, triazines, benzotriazoles or benzophenones. Combinations of several anti-UV agents can be used to obtain better UV resistance. Examples of UV used include TINUVIN ® 770, Tinuvin ® 328, Tinuvin ® P or TINUVIN ® 234.
  • ASA copolymer acrylic-styrene-acrylonitrile sold by GE PLASTICS particular under the trademark GELOY ®
  • polystyrene crystal or shock
  • the multilayer structure comprises in the order: a protective layer (I) comprising a PMMA, optionally a pigmented layer (II), an intermediate ductile layer (III) comprising a block copolymer of formula BA n composed of: polymer block B comprising by weight at least 60% of at least one (meth) acrylic monomer having a T 9 lower than -5 ° C., and - n polymer A sequences, linked to the polymer block B by covalent bonds, n denotes an integer between 1 and 10, comprising by weight at least 60% of at least one (meth) acrylic monomer having a T g greater than 0 ° C.,
  • a pigmented layer (II) can be placed between the protective layer (I) and the intermediate ductile layer (III).
  • the pigmented layer (II) comprises at least one pigment dispersed in a thermoplastic resin which is preferably a PMMA. The proportion of pigment varies from 1 to 50 parts of pigment per 100 parts of acrylic polymer.
  • the protective layer (I) has a thickness of between 10 and 500 ⁇ m, preferably between 50 and 200 ⁇ m.
  • the intermediate ductile layer (II) has a thickness of between 100 and 1000 ⁇ m, preferably between 100 and 400 ⁇ m.
  • the optional pigmented layer (II) has a thickness of between 10 and 80 ⁇ m, preferably between 10 and 50 ⁇ m.
  • the set of layers (I), (II) and (III) may have a thickness greater than 310 microns.
  • the multilayer structure can be obtained by hot compression of the layers (I) to (IV).
  • a multi-injection technique consisting of injecting into the same mold the melts constituting the layers.
  • the molten materials are injected simultaneously into the mold.
  • a 2nd technique a movable insert is located in the mold. By this insert, a melt is injected into the mold, and then the moving insert is moved to inject another melt.
  • the preferred technique is coextrusion which relies on the use of as many extruders as there are layers to extrude. This technique is more flexible than the previous ones and makes it possible to obtain multilayer structures even for complicated geometries, for example profiles. It also allows to have excellent mechanical homogeneity.
  • the coextrusion technique is a known technique in thermoplastics processing (see, for example, Precis of Plastics, Structures-Properties, 1989, Implementation and Standardization 4th Edition, Nathan, 126). US 5318737 discloses an example of coextrusion with a structural plastic.
  • the method consists in protecting a structural plastic by superimposing in the order by coextrusion, hot compression or multiinjection: • a protective layer (I) comprising a PMMA, • optionally a pigmented layer (II), • an intermediate ductile layer (III) comprising a block copolymer of the formula BA n composed of: a polymer block B comprising by weight at least 60% of at least one (meth) acrylic monomer having a T g lower than -5 ° C., and n sequences polymer A, linked to the polymer block B by covalent bonds, n denoting an integer of between 1 and 10, comprising by weight at least 60% of at least one (meth) acrylic monomer having a T g greater than 0 ° C. • a layer of the structural plastic (III).
  • PVC is advantageously used as structural plastic in the manufacture of parts which are intended for exterior applications such as building doors, gutters, window moldings or cladding.
  • the degradation of PVC under the effect of UV rays causes a color change (especially in dark shades such as blue or black) and / or decreased resistance to impact.
  • PVC panels generally contain as a UV stabilizer titanium dioxide which also acts as a white pigment.
  • the proportion of titanium dioxide is generally of the order of 3%, which makes it difficult to obtain dark shades. Panels can only be dyed in light or pastel shades.
  • the invention solves the problem of coloring and / or UV protection of PVC outer facade panels while preserving the impact resistance of PVC.
  • the invention therefore also relates to an exterior facade panel comprising in order:
  • a protective layer (I) comprising a PMMA, optionally a pigmented layer (II),
  • a layer of PVC the layers being arranged one above the other in the order (I) to (IV) indicated.
  • the multilayer structures were made on a trilayer co-extrusion line AMUT brand.
  • a lamella layer distribution block was used for coextrusion and a 650 mm wide coat rack. Calibration of the structure was carried out on a vertical grille consisting of three independently thermoregulated rolls.
  • the ABS is extruded at a temperature between 245 and 255 0 C using a 70 mm diameter machine, length equal to 32D provided with a degassing well.
  • the extruder used for the layer of the triblock copolymer has a diameter of 30 mm and a length of 24D.
  • the temperature is regulated at approximately 250 ° C.
  • the surface PMMA is extruded with an extruder with a diameter of 30 mm and a length of 25 ° C. at a temperature of approximately 250 ° C. as well.
  • Resilience expressed in kJ / m 2 , is measured on ABS specimens protected or not by an acrylic protective layer. Resilience is measured using a fast bending test. The specimen is flexed in the middle of the span at a constant speed.
  • the load applied to the specimen is measured.
  • the bending test is carried out at constant speed on the MTS-831 servo-hydraulic equipment.
  • the force is measured by means of a piezoelectric cell embedded in the nose of the striker 569.4 N.
  • the displacement of the specimen during the stress is measured by an LVDT sensor on the hydraulic cylinder of 50 mm range.
  • the specimen dimensions are:
  • the triblock copolymer 1 is prepared by bulk polymerization. 6000 g of butyl acrylate, 35 g of the DIAMS alkoxyamine and 1 g of SG1 nitroxide are introduced into a metal reactor equipped with mechanical stirring and a jacket. The temperature of the mixture is raised to 115 ° C. After 225 minutes, the conversion is 60% and the butyl polyacrylate has a number average weight of 66960 g / mol, by weight of 128300 g / mol and a polymolecularity index of 1.9.
  • the viscous mixture temperature is 90 0 C.
  • a product composed of PMMA-b-poly (butyl acrylate) -PMMA is thus obtained.
  • the copolymer is prepared in suspension in water.
  • the polymer resulting from the polymerization of 2-acrylamido-2-methylpropanesulphonic acid neutralized with NaOH sodium hydroxide is used as dispersing agent.
  • the dispersing agent is prepared according to Example 1 of US Pat. No. 5,733,992; it has a Brookfield viscosity of 4 Pa.s at 25 ° C.
  • the dispersing agent is designated by PAMS in the following examples.
  • the reaction mixture is brought to 100 ° C. for a period of 2 hours at the end of which a mixture of 3.7 g of octyl mercaptan diluted in 11.2 g of MMA is introduced.
  • the reaction mixture is stirred at 100 ° C. for 1 hour.
  • a solution of 1.35 g of Luperox ® 26R in 11.2 g of MMA mounting the reactor temperature to 105 0 C and held for 1 hour.
  • the suspension is then cooled, filtered using a wringer, plumped with 7000 g of water, and then dewatered again. This is done 3 times.
  • the triblock copolymer 2 is in the form of beads composed of PMMA-b-poly (butyl acrylate) -b-PMMA, with a mean diameter of 334 ⁇ m.
  • Triblock Copolymer 3 Step 1 Preparation of a solution comprising living butyl polyacrylate and deactivated butyl polyacrylate in MMA
  • butyl acrylate In a 20 liter reactor stirred at 200 rpm, 14000 g of butyl acrylate are polymerized at 117 ° C. in the presence of 140 g of DIAMINS to a conversion rate of 70%, measured by dry extract.
  • Butyl polyacrylate has the following molecular weights in PMMA equivalent: average mass at the peak: 97220 g / mol average mass by number: 67810 g / mol average mass by weight: 106990 g / mol average mass in z: 148020 g / mol polymolecularity 1.6
  • 4240 g of the above mixture is heated (that is to say comprising polybutyl acrylate and butyl acrylate) at 7O 0 C in the presence of 13.7 g AIBN 1 diluted in 30 g of butyl acrylate.
  • An exotherm of approximately 25 ° C. is observed, that is to say that the temperature in the reactor increases to 95 ° C., then the reaction medium is maintained at 70 ° C. for 6 hours and then cooled to 30 ° C. 0 C, and diluted with MMA to obtain a solution comprising 45% by weight of butyl polyacrylate.
  • This butyl polyacrylate corresponds to living butyl polyacrylate, that is to say reactivatable, and deactivated butyl polyacrylate.
  • step 2 preparation of the triblock copolymer 3 7000 g of deionized water, 509 g of a 5.3% solution of PAMS and 0.37 g of sodium hydroxide are charged into a 20-liter reactor which has been degassed before and is purged with nitrogen. This solution is brought to 70 ° C. with stirring at 200 rpm. When the temperature reaches 70 ° C., a solution of 4218 g of the solution prepared in the previous step 1 is poured.
  • the reaction mixture is brought to 100 ° C. for a period of 2 hours at the end of which a mixture of 3.7 g of octyl mercaptan diluted in 11.2 g of MMA is introduced.
  • the reaction mixture is stirred at 100 0 C for 1 hour, then continuous way of introducing a mixture of 6.75 g of Luperox ® 26R and 247 g of MMA for 1 hour, then 1.35 g of Luperox ® 26R in 11.25 g of MMA, and the temperature of the reactor is raised to 105 0 C for 1 hour.
  • the suspension is then cooled, filtered using a wringer, plumped with 7000 g of water and then dewatered again. This is done 3 times.
  • the triblock copolymer 3 is in the form of beads composed of a mixture of PMMA-b-poly (butyl acrylate) -PMMA and poly (butyl acrylate), with a mean diameter of 168 ⁇ m.
  • Figure 4 shows an AFM image of the product obtained. We notice that it has a nanostructuration (phase microseparation) with phases (see the points that appear in clear) whose size is less than 100 nm (the scale of the plate is 5 microns).
  • reaction mixture is brought to 100 ° C. for a period of 2 hours, after which a mixture of 3.7 g of octyl mercaptan diluted in 11.2 g of
  • the suspension is then cooled, filtered using a wringer, plumped with 7000 g of water and then dewatered again. This is done 3 times.
  • the copolymer triblock 2 is in the form of beads whose average size is 209 microns. The triblock copolymer is then granulated.
  • ABS alone has a resilience of 50.6 kJ / m 2 (ex.l). It drops when the ABS is covered by ALTUGLAS ® VO44 or DRT (ex.2 and 3).
  • the structure of the ex. 10 has a high UV resistance thanks to TINUVIN ® P.
  • ABS MAGNUM 3904 marketed by DOW, having a melt index of 1, 5 g / 10 min (23 O 0 C, 3, 8 kg) - thickness 3 mm

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  • Graft Or Block Polymers (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
EP05818155A 2004-11-17 2005-11-17 Capstock acrylique Withdrawn EP1812235A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0412172 2004-11-17
PCT/FR2005/002855 WO2006053984A1 (fr) 2004-11-17 2005-11-17 Capstock acrylique

Publications (1)

Publication Number Publication Date
EP1812235A1 true EP1812235A1 (fr) 2007-08-01

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Family Applications (1)

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EP05818155A Withdrawn EP1812235A1 (fr) 2004-11-17 2005-11-17 Capstock acrylique

Country Status (9)

Country Link
EP (1) EP1812235A1 (ja)
JP (1) JP2008520468A (ja)
KR (1) KR20070088668A (ja)
CN (1) CN101102894A (ja)
BR (1) BRPI0518428A2 (ja)
CA (1) CA2588136A1 (ja)
MX (1) MX2007005860A (ja)
RU (1) RU2007122492A (ja)
WO (1) WO2006053984A1 (ja)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2941704B1 (fr) 2009-01-30 2011-12-23 Arkema France Copolymeres a blocs porteurs de groupes associatifs et adhesif les comprenant
CN102529264A (zh) * 2012-01-17 2012-07-04 苏州禾盛新型材料股份有限公司 Hips复合板材
US9127113B2 (en) * 2012-05-16 2015-09-08 Rohm And Haas Electronic Materials Llc Polystyrene-polyacrylate block copolymers, methods of manufacture thereof and articles comprising the same
US20200291214A1 (en) * 2016-03-25 2020-09-17 Arkema France Enhanced melt strength thermoplastic formulation
EP3473497B1 (en) 2017-10-17 2021-11-03 SABIC Global Technologies B.V. Front end panel for an electric vehicle

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000504043A (ja) * 1996-01-25 2000-04-04 ビーエーエスエフ アクチェンゲゼルシャフト ブロック共重合体
FR2852961B1 (fr) * 2003-03-26 2006-07-07 Atofina Nouveau procede de synthese/fabrication de films acryliques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006053984A1 *

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Publication number Publication date
CN101102894A (zh) 2008-01-09
JP2008520468A (ja) 2008-06-19
KR20070088668A (ko) 2007-08-29
WO2006053984A1 (fr) 2006-05-26
BRPI0518428A2 (pt) 2008-11-25
MX2007005860A (es) 2007-07-20
CA2588136A1 (fr) 2006-05-26
RU2007122492A (ru) 2008-12-27

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